KR20220043155A - Purification process of polyether polyols - Google Patents

Abstract

Treating the polyether polyol with a mixture of (i) a sulfonic acid catalyst, which is a catalyst comprising a substituted or unsubstituted alkyl group of at least 6 carbon atoms, and (ii) water to reduce residual levels of acetal linkages present in the polyether polyol A process comprising the step of; purified polyether polyols prepared using the above treatment process; and a polyurethane product prepared by reacting the purified polyether polyol with an isocyanate.

Description

Purification process of polyether polyols

An embodiment relates to a process for the purification of polyether polyols. More specifically, exemplary embodiments relate to a process for treating a polyether polyol with a sulfonic acid catalyst to reduce residual levels of acetal linkages present in the polyether polyol.

introduction

In the Lewis acid-catalyzed ring-opening polymerization of alkylene oxides, aldehydes are inevitably produced as small amounts of by-products. It is known to those skilled in the art that the presence of aldehydes causes a condensation reaction with the polyol to produce the by-product polyether acetal polyol. The presence of such polyether acetal polyols in polyether polyols may be undesirable in certain applications, as these acetals produce a bimodal molecular weight distribution that is biased towards higher molecular weight. In addition, hydrolysis of polyether acetal polyols may release aldehydes in the end-use, which will cause undesirable odors. Many prior art references describe acid finishing of polyols from which these polyols are produced using well-known basic alkoxylation catalysts. For example, US Pat. No. 5,095,061 describes a process for treating a neutralized polyol with an acid catalyst and water to reduce the concentration of alkenyl end groups in the polyol. Similarly, US Pat. No. 6,504,062 describes the preparation of low odor polyether polyols by acid finishing of unneutralized (ie, basic) polyols. Excess acid is added to the polyol to neutralize the residual basic alkoxylation catalyst and yield a free acid capable of catalyzing the hydrolysis of alkenyl end groups and cyclic ether impurities in the presence of water. In each case, the polyol produced by the basic alkoxylation catalyst is treated with an acid catalyst and water to hydrolyze the by-products produced by the basic alkoxylation catalyst. However, only a few prior art documents describe acid finishing of polyols from which these polyols are prepared using Lewis acids.

For example, JP05763734B2 describes the preparation of low brittle polyether polyols through the use of a Lewis acidic alkoxylation catalyst followed by acid finishing. This reference describes the use of water and residual Lewis acid alkoxylation catalysts and, optionally, additional Lewis acid or Brønsted acid catalysts for the acid finishing process. This reference discloses that suitable Bronsted acids used in the process include sulfuric acid, hydrochloric acid, phosphoric acid and alkylsulfonic acids, and phosphoric acid is exemplified by the Bronsted acid used. However, this reference does not teach whether the mixture of water and polyether polyol is monophasic or biphasic under the conditions of the acid finishing process. Also, while this reference specifies an autoclave in the examples described in the reference, the reference does not teach how effective mixing of the reaction mixture is achieved. Under two-phase conditions due to the immiscibility of polyol and water, inefficient mixing of polyol and water in the presence of a Lewis acid catalyst and, optionally, a Bronsted acid catalyst, can lead to incomplete acid finish and/or prolonged treatment times may be needed In addition, although sulfuric acid, hydrochloric acid, phosphoric acid and alkylsulfonic acid are defined as suitable Brønsted acid catalysts in the above reference, only a single example using phosphoric acid is described in the reference.

summary

Embodiments relate to processes for the purification of polyether polyols produced with Lewis acid alkoxylation catalysts to reduce residual levels of acetal linkages present in the polyether polyols. In one general embodiment, the process comprises a polyether polyol (i) a sulfonic acid catalyst, which is a catalyst comprising a chain length of carbon atoms of at least 6 carbon atoms, for example at least 6 carbon atoms to 18 carbon atoms (C6 to C18) a catalyst comprising a substituted or unsubstituted alkyl group; and (ii) purifying the polyether polyol by treating the polyether polyol with a mixture that is water to reduce residual levels of acetal linkages present in the polyether polyol. In an exemplary embodiment, the polyether polyol comprises (i) a C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid catalyst and (ii) a residual level of acetal linkages that form a biphasic polyol and water mixture and are present in the polyether polyol. It can be treated with water to reduce // p4 line 25

In some embodiments, treating a biphasic mixture of polyether polyol and water with a C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid catalyst at a temperature of 60°C to 140°C; and less than 0.005 moles (<) of sulfonic acid per kg polyether polyol at C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid catalyst concentrations induce acetal bond hydrolysis with the required reaction time of less than 30 minutes (minutes) . In some embodiments, for example, when the temperature is 80° C. to 140° C. and the sulfonic acid concentration per kg polyether polyol is <0.005 mole sulfonic acid, acetal hydrolysis requires a reaction time of (≤) 5 minutes or less.

Advantageously, the reduced reaction time reduces the concentration of undesirable by-products formed from the condensation reaction of propionaldehyde produced during the hydrolysis reaction. Compared to sulfonic acids without C6 to C18 alkyl substituents, the present invention reduces the reaction time required for the hydrolysis reaction to be completed by an exemplary Brønsted acid catalyst, C6 to C18 alkylsulfonic acids or C6 to C18 alkylated arylsulfonic acids, by at least 20%. taught to reduce The improved hydrolysis rate of the process of the present invention advantageously reduces cycle times in the process and facilitates the production of higher volumes of acid-finished polyols. The improved rate of hydrolysis is an unexpected result because C6 to C18 alkylsulfonic acids and C6 to C18 alkylated arylsulfonic acids are not much more acidic than other sulfonic acids without C6 to C18 alkyl substituents.

1 is a GPC chromatography showing two peaks, one peak representing the concentration of component A (generally indicated by arrow A) and the other peak representing the concentration of component B (generally indicated by arrow B); A graphical illustration of a GPC chromatogram, wherein component A is the undesirable polyether acetal polyol component and component B is the preferred polyether polyol product component.

As used throughout this specification, unless the context clearly dictates otherwise, the abbreviations given below have the following meanings: μm = micron(s), g = gram(s); mg = milligram(s); L = liter(s); mL = milliliter(s); ppm = parts per million; ppmw = parts per million by weight; rpm = revolutions per minute; m = meter(s); mm = millimeter(s); cm = centimeter(s); min = minute(s); s = seconds(s); hr = time(s); °C = degree Celsius(s); % = percent, vol % = volume percent; and wt% = weight percent.

The term “polyether polyol” refers to a reaction product formed by the addition of an epoxide to a compound containing active hydrogen atoms.

The term "polyether acetal polyol" refers to a polyether polyol containing linear acetal linkages represented by the general formula (I):

wherein R ¹ is an alkyl group, and R ² and R ³ represent polyether chains of the general formula (II):

In the above formula, R ⁴ is H or an alkyl group and n is an integer.

As used herein, the term "C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid" refers to an acid catalyst containing a sulfonic acid and a substituted or unsubstituted alkyl group having 6 to 18 carbon atoms.

The term "alkylsulfonic acid" herein refers to a sulfonic acid catalyst containing a substituted or unsubstituted alkyl group.

As used herein, the term “arylsulfonic acid” refers to a sulfonic acid catalyst containing a substituted or unsubstituted aryl group including a phenyl group, a naphthyl group, and the like.

Production of polyether polyols

Processes for the production of polyether polyols are well known processes and are described in several documents including, for example, US Pat. Nos. US 9,896,542, US 7,378,559 and US 5,374,705. In general, producing a polyether polyol comprises the steps of (1) feeding an initiator having a nominal hydroxyl functionality of at least 1 to a reactor; (2) feeding one or more monomers, such as alkylene oxide, to the reactor; (3) feeding a polymerization catalyst such as a Lewis acid catalyst to the reactor; (4) optionally, feeding a hydrogen bond acceptor additive to the reactor separately from feeding the initiator to the reactor; and (5) allowing the initiator to react with one or more monomers in the presence of the polymerization catalyst and optionally the hydrogen bond acceptor additive to form a polyether polyol. Embodiments relate to further purification of the resulting polyether polyol, for example to reduce residual levels of acetal linkages present in the polyether polyol.

In an exemplary embodiment, the polymerization catalyst is a Lewis acid polymerization catalyst. For example, the Lewis acid polymerization catalyst has the general formula (III):

wherein M is boron, aluminum, indium, bismuth or erbium; R ¹ comprises (eg, consists of) a first fluoro/chloro or fluoroalkyl-substituted phenyl group; R ² comprises (eg, consists of) a second fluoro/chloro or fluoroalkyl-substituted phenyl group; R ³ comprises (eg, consists of) a third fluoro/chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group; Optional R ⁴ is (eg, consists of) a second functional group or a functional polymer group.

As used herein, "fluoro/chloro or fluoroalkyl-substituted phenyl group" means that a fluoro/chloro substituted phenyl group or a fluoroalkyl-substituted phenyl group is present, as described below. "Fluoroalkyl-substituted phenyl group" means a phenyl group comprising at least one hydrogen atom replaced with a fluoroalkyl group. "Fluoro-substituted phenyl group" means a phenyl group comprising at least one hydrogen atom replaced by a fluorine atom. "Chloro-substituted phenyl group" means a phenyl group comprising at least one hydrogen atom replaced by a chlorine atom. "Fluoro/chloro-substituted phenyl group" means a phenyl group comprising at least one hydrogen atom replaced with a fluorine or chlorine atom, wherein the phenyl group may include a combination of fluorine and chlorine atom substituents.

In general formula (III), R ¹ , R ² and R ³ can each independently comprise a fluoro/chloro or fluoroalkyl-substituted phenyl group, or each independently is essentially a fluoro/chloro or fluoroalkyl group - may consist of a substituted phenyl group. M in general formula (III) may exist as a metal salt ion or as an integrally bound moiety of general formula (III).

With respect to R ³ and optional R ⁴ , the functional group or functional polymeric group may include (1) a Lewis base to form a complex with a Lewis acid catalyst (eg, a boron-based Lewis acid catalyst); and/or (2) a molecule or moiety containing at least one electron pair available to form a dative bond with a Lewis acid. The Lewis base may be a polymeric Lewis base. By “functional group” or “functional polymeric group” is meant a molecule containing at least one of those described below: water, alcohol, alkoxy (including, for example, linear or branched ethers and cyclic ethers), ketones, Esters, organosiloxanes, amines, phosphines, oximes and substituted analogs thereof. Each alcohol, linear or branched ether, cyclic ether, ketone, ester, alkoxy, organosiloxane, and oxime is, for example, from 2 carbon atoms to 20 carbon atoms in one embodiment, and 2 carbon atoms in another embodiment. from 2 carbon atoms to 12 carbon atoms, in still another embodiment from 2 carbon atoms to 8 carbon atoms, and/or from 3 carbon atoms to 6 carbon atoms in yet another embodiment.

For example, a functional group or functional polymer group may have the general formula (OYH)n, wherein O is O oxygen, H is hydrogen, Y is H or an alkyl group, and n is an integer (e.g., an integer from 1 to 100). However, other known functional polymer groups that can be combined with a Lewis acid catalyst such as a boron-based Lewis acid catalyst may be used. Exemplary cyclic ethers include tetrahydrofuran and tetrahydropyran. Polymeric Lewis bases are moieties containing two or more Lewis base functional groups, such as polyols and polyethers based on polymers of ethylene oxide, propylene oxide and butylene oxide. Exemplary polymeric Lewis bases are ethylene glycol, ethylene glycol methyl ether, ethylene glycol dimethyl ether, diethylene glycol, diethylene glycol dimethyl ether, triethylene glycol, triethylene glycol dimethyl ether, polyethylene glycol, polypropylene glycol, and polybutyl Contains ren glycol.

Without intending to be bound by this theory, when utilized in polymerization reactions, certain R ⁴ may, for example, help improve the shelf life of the catalyst without significantly impairing catalyst activity. For example, a catalyst comprising M, R ¹ , R ² , and R ³ can be in the form (M(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ (R ⁴ ) ₁ form with an optional R ⁴ . ) or without the optional R ⁴ (M(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ form). Suitable R ⁴ groups that can help increase catalyst storage stability without impairing catalyst activity, for example, are diethyl ether, cyclopentyl methyl ether, methyl tert -butyl ether, tetrahydrofuran, 2-methyltetrahydro furan, tetrahydropyran, 1,4-dioxane, acetone, methyl isopropyl ketone, isopropyl acetate and isobutyl acetate.

According to an exemplary embodiment, the Lewis acid catalyst is a boron-based Lewis acid catalyst having the general formula B(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ (R ⁴ ) _{0 or 1} , wherein R ¹ , R ² , and R ³ are each independently a fluoroalkyl-substituted phenyl group, and optionally R ⁴ is a functional group or a functional polymer group.

According to an exemplary embodiment, the Lewis acid catalyst has the general formula M(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ (R ⁴ ) _{0 or 1} , wherein M is boron, aluminum, indium, bismuth. or erbium, R ¹ , R ² , and R ³ are each a fluoroalkyl-substituted phenyl group, and optional R ⁴ is a functional group or functional polymer group discussed above. In the above general formula, M may exist as a metal salt ion or an integrally bonded moiety of the formula. R ¹ , R ² and R ³ may each independently be a phenyl group substituted with fluoroalkyl. For example, R ¹ , R ² and R ³ can each be a phenyl group substituted with the same fluoroalkyl. R ¹ , R ² and R ³ may comprise a fluoroalkyl-substituted phenyl group or may consist essentially of a fluoroalkyl-substituted phenyl group. Similarly, R ⁴ may comprise a functional group or functional polymer group, or R ⁴ may consist essentially of a functional group or functional polymer group. With respect to R ¹ , R ² and R ³ , a fluoroalkyl-substituted phenyl group refers to a phenyl group comprising at least one hydrogen atom replaced with a fluoroalkyl group which is an alkyl group having at least one hydrogen atom replaced with a fluorine atom. it means. For example, a fluoroalkyl group can have the structure C _n H _m F _2n+1-m , where n is greater than 1 and less than 5. Also, m is a number reflecting the balance of charges to provide an overall electrostatically neutral compound, and may be, for example, 0, 1, or greater than 1.

The phenyl group of a fluoroalkyl-substituted phenyl may be substituted to contain other groups other than at least one fluoroalkyl group, for example, a fluorine atom and/or a chlorine atom replacing at least one hydrogen of the phenyl group. For example, R ¹ , R ² and R ³ are a fluoro/chloro-fluoroalkyl-substituted phenyl group meaning that one fluoro or chloro group and at least one fluoroalkyl group are substituted on the phenyl group ), a difluoro/chloro-fluoroalkyl-substituted phenyl group (meaning two fluoro, two chloro or one fluoro and chloro groups and at least one fluoroalkyl group are substituted on the phenyl group) , a trifluoro/chloro-fluoroalkyl-substituted phenyl group (3 fluoro, 3 chloro or a combination of a total of 3 fluoro and chloro groups, and at least one fluoroalkal group is substituted on the phenyl group means), or a tetrafluoro/chloro-fluoroalkyl-substituted phenyl group (four fluoro, four chloro or a combination of four fluoro and chloro groups in total, and one fluoroalkyl group on the phenyl group means to be substituted for). When present, the functional group or functional polymeric group R ⁴ forms a coordination bond with a Lewis acid and/or a Lewis base that forms a complex with a Lewis acid catalyst (eg, a boron-based Lewis acid catalyst) as discussed above. It may exist as a molecule or moiety containing at least one electron pair available for

According to another exemplary embodiment, the Lewis acid catalyst has the general formula M(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ (R ⁴ ) _{0 or 1} , wherein M is boron, aluminum, indium, bismuth or erbium, R ¹ comprises a first fluoroalkyl-substituted phenyl group, R ² is a second fluoroalkyl-substituted phenyl group or a first fluoro-substituted phenyl group or chloro-substituted phenyl a group (ie, a fluoro/chloro or fluoroalkyl-substituted substituted phenyl group), wherein R ³ is a third fluoroalkyl-substituted phenyl group or a second fluoro-substituted phenyl group or chloro- substituted phenyl groups (ie, fluoro/chloro or fluoroalkyl-substituted substituted phenyl groups), wherein optional R ⁴ is a functional group or a functional polymeric group. In the above general formula, M may exist as a metal salt ion or as an integrally bonded moiety of the formula. R ¹ , R ² , R ³ and R ⁴ are each independently, for example, the fluoroalkyl-substituted phenyl group of R ¹ can be the same as or different from the fluoroalkyl-substituted phenyl group of R ² . However, R ¹ is R ² and R ³ R ¹ is different from at least one of R ² and R ³ such that each is not all the same (eg, the same fluoroalkyl-substituted phenyl group), and R ¹ is not the same as or identical to R ² or R ³ . it may not be

R ¹ may comprise or consist essentially of the first fluoroalkyl-substituted phenyl group. Similarly, R ² may comprise a second fluoroalkyl-substituted phenyl group or a first fluoro/chloro-substituted phenyl group, or essentially a second fluoroalkyl-substituted phenyl group or a first fluoro /chloro-substituted phenyl groups. Similarly, R ³ may comprise a third fluoroalkyl-substituted phenyl group or a second fluoro/chloro-substituted phenyl group, or essentially a third fluoroalkyl-substituted phenyl group or a second fluoro /chloro-substituted phenyl groups. Similarly, R ⁴ may comprise a functional group or a functional polymer group, or R ⁴ may consist essentially of a functional group or a functional polymer group.

With respect to R ¹ , R ² and R ³ , a fluoroalkyl-substituted phenyl group is an alkyl group having at least one hydrogen atom replaced with a fluorine atom, a phenyl group comprising at least one hydrogen atom replaced with a fluoroalkyl group it means. For example, a fluoroalkyl group can have the structure C _n H _m F _2n+1-m , where n is greater than 1 or less than 5. Also, m is a number reflecting the balance of charges to provide an overall electrostatically neutral compound, and may be, for example, 0, 1 or greater than 1. The phenyl group of a fluoroalkyl-substituted phenyl may be substituted to contain other groups other than at least one fluoroalkyl group, for example, a fluorine atom and/or a chlorine atom replacing at least one hydrogen of the phenyl group. For example, R ¹ , R ² , or R ³ is a fluoro/chloro-fluoroalkyl-substituted phenyl group (meaning one fluoro or chloro group and at least one fluoroalkyl group are substituted on the phenyl group ), a difluoro/chloro-fluoroalkyl-substituted phenyl group, meaning that two fluoro, two chloro or one fluoro and chloro groups, and at least one fluoroalkyl group are substituted on the phenyl group ), a trifluoro/chloro-fluoroalkyl-substituted phenyl group (3 fluoro, 3 chloro or a combination of a total of 3 fluoro and chloro groups, and at least one fluoroalkyl group on the phenyl group means substituted), or a tetrafluoro/chloro-fluoroalkyl-substituted phenyl group (four fluoro, four chloro or a combination of four fluoro and chloro groups in total, and one fluoroalkyl group is phenyl means substituted on the group).

With reference to R ² and R ³ , a fluoro-substituted phenyl group means a phenyl group comprising at least one hydrogen atom replaced by a fluorine atom. A chloro-substituted phenyl group means a phenyl group comprising at least one hydrogen atom replaced by a chlorine atom. The phenyl group of a fluoro/chloro-substituted phenyl group may be substituted with other groups (e.g., which may include combinations of fluoro, chloro and/or hydrogen), except for any fluoroalkyl group (e.g. eg, except for groups having the structure C _n H _m F _2n+1-m discussed above). Thus, a fluoro/chloro-substituted phenyl group is distinguished from a fluoroalkyl-substituted phenyl group by excluding any fluoroalkyl group substituted on the phenyl ring. With respect to optional R ⁴ , the functional group or functional polymeric group forms a coordination bond with a Lewis base and/or a Lewis acid that forms a complex with a Lewis acid catalyst (eg, a boron-based Lewis acid catalyst) as discussed above. It may be a molecule or moiety containing at least one electron pair available to

In this regard, exemplary embodiments may utilize blends of catalysts using, for example, one or more of the above catalyst structures. The Lewis acid catalyst used in the exemplary embodiment comprises one or more Lewis acid catalysts (eg, each having the general formula B(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ (R ⁴ ) _{0 or 1} ). having) and optionally at least one other catalyst (eg, such as catalysts known in the art for producing polyether polyols). The combination catalyst may optionally include other catalysts, wherein one or more Lewis acid catalysts having the general formula B(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ (R ⁴ ) _{0 or 1} are account for at least 25% by weight, at least 50% by weight, at least 70% by weight, at least 75% by weight, at least 80% by weight, at least 85% by weight, at least 90% by weight, at least 95% by weight, at least 99% by weight, etc. do. The blended catalyst added may include or exclude any DMC-based catalyst. Exemplary other metallic Lewis acids that are activated at lower temperatures may be included as part of dual catalyst systems and/or combination catalysts. Exemplary metallic Lewis acids are based on one of aluminium, boron, copper, iron, silicon, tin, titanium, zinc, and zirconium.

refining process

Upon completion of the reaction process to produce the polyether polyol product as described above, acetal linkages are formed in the polyether polyol and these acetal linkages form the purified polyol for use in various applications requiring the purified polyether polyol. It may need to be removed from the polyether polyol to obtain the ether polyol. Accordingly, in one broad embodiment, the present invention comprises a process for purifying a polyether polyol to reduce residual levels of acetal linkages present in the polyether polyol, the process comprising preparing a mixture of polyether polyol and water from C6 to and treatment with a C18 alkylsulfonic acid or a C6 to C18 alkylated arylsulfonic acid catalyst.

In an exemplary embodiment, the chemical structure of the sulfonic acid catalyst may include, for example, the following general chemical structure:

R ⁵ -SO ₃ H,

In the above formula, R ⁵ represents a substituted or unsubstituted alkyl group having 6 to 18 carbon atoms.

In another exemplary embodiment, the chemical structure of the sulfonic acid catalyst may include, for example, the following general chemical structure:

R ⁵ -ArSO ₃ H

In the above formula, R ⁵ represents a substituted or unsubstituted alkyl group having 6 to 18 carbon atoms, and Ar represents a substituted or unsubstituted aryl group including, for example, phenyl and naphthyl.

Component (i) useful in the present invention, C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid catalyst is, for example, hexylbenzene sulfonic acid, octylbenzene sulfonic acid, decylbenzene sulfonic acid, dodecylbenzene sulfonic acid, hexanesulfonic acid, octane sulfonic acid, decanesulfonic acid, dodecanesulfonic acid, tetradecanesulfonic acid, hexadecanesulfonic acid, octadecanesulfonic acid, and mixtures thereof.

In one exemplary embodiment, the sulfonic acid catalyst useful in the present invention may be dodecylbenzene sulfonic acid and a mixture of dodecylbenzene sulfonic acid with other sulfonic acids.

The concentration of sulfonic acid, which is component (i) useful in the process of the present invention, may be, for example, in one embodiment from 0.0001 moles of sulfonic acid per kg of polyether acetal polyol to 0.005 moles of sulfonic acid per kg of polyether polyol, in another embodiment the polyether polyol. from 0.0001 moles of sulfonic acid per kg of ether polyol to 0.0025 moles of sulfonic acid per kg of polyether polyol, in still another embodiment from 0.0001 moles of sulfonic acid per kg of polyether polyol to 0.001 moles of sulfonic acid per kg of polyether polyol.

Water, as component (ii) used in the present invention, may comprise, for example, deionized water. In general, the concentration of water, which is useful component (ii) in the process of the present invention, is, for example, from 0.1% to 20% by weight in one embodiment, from 0.5% to 10% by weight in another embodiment, and still further in other embodiments from 0.5% to 5.0% by weight.

As described above, the process for purifying polyether polyols of the present invention comprises the steps of: (A) treating with a mixture of (i) polyether polyol and (ii) water having a C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid catalyst; and (B) heating the mixture. The process steps are carried out, for example, at a temperature of from 60 °C to 140 °C in one embodiment, from 80 °C to 120 °C in another embodiment, and from 80 °C to 100 °C in still another embodiment. And, the reaction time of the process steps may be, for example, less than 30 minutes in one embodiment; 1 minute to 10 minutes in another embodiment; and reaction times of from 1 minute to 5 minutes in still another embodiment.

The purification process of the present invention provides several advantageous properties and/or advantages. For example, the process allows the use of: (1) a low concentration of C6 to C18 alkylsulfonic acid or a low concentration of C6 to C18 alkylated arylsulfonic acid catalyst; (2) can be carried out at mild reaction temperatures; (3) It provides a short reaction time.

For example, the C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid concentration used in the process of the present invention ranges from 0.0001 moles of sulfonic acid per kg of polyether polyol to per kg of polyether polyol in one general embodiment as described above. containing a concentration of 0.005 moles of sulfonic acid.

For example, the reaction temperature used in the process of the present invention includes a temperature between 60° C. and 140° C. in one general embodiment as described above.

For example, reaction times used in the process of the present invention include reaction times of less than 30 minutes in one general embodiment, for example as described above.

The polyol product produced after undergoing the purification treatment of the present invention has a residual concentration of polyether acetal polyol of ≤ 5.0 wt % in one embodiment, ≤ 3.0 wt % in another embodiment, and ≤ 1.0 wt % in still another embodiment. %am. In another embodiment, the residual concentration of polyether acetal polyol is greater than 0.01 wt% (>) in one embodiment, greater than 0.1 wt% in another embodiment, and greater than 1 wt% in still another embodiment. In an exemplary embodiment, the residual concentration of the polyether acetal polyol is between 1.0% and 5.0% by weight. The residual concentration of polyether acetal polyol present in the polyether polyol is determined by gel permeation chromatography (GPC).

In one embodiment, polyether polyols are used to react polyols with isocyanates to produce polyurethane products.

Example

The following examples are presented to illustrate the invention in further detail, but should not be construed as limiting the scope of the claims. Unless otherwise indicated, all parts and percentages are by weight.

Various terms and names used in the inventive example (Inv. Ex.) and the comparative example (Comp. Ex.) of the present invention are explained as follows:

"PDI" means polydispersity index.

"M _N " means number-average molecular weight.

"M _W " means weight-average molecular weight.

"GPC" means gel permeation chromatography.

"DBSA" means dodecylbenzene sulfonic acid.

"BSA" means benzenesulfonic acid.

"Temp." means temperature.

"Min" means minutes.

"wt %" means weight percent based on the total mass of the reaction solution.

"RPM" means revolutions per minute.

"Pa" stands for Pascal, a unit of pressure.

Various raw materials or materials used in the inventive example (Inv. Ex.) and the comparative example (Comp. Ex.) of the present invention are described in Table I as follows:

Table I - Acids used in the Examples

Polyether acetal polyol concentration of polyether polyol test method

GPC analysis is performed using an inline vacuum degasser, liquid autosampler, a binary pump, a thermostated column compartment, a thermostat, a refractive index (RI) detector, PLgel A 5-μm guard column (50 mm x 7.5 mm) and a series of four PLgel 5-μm (300 mm x 7.5 mm) narrow porosity analytical columns (e.g., 50 Å; 100 Å; 1,000 Å; and 10,000 Å) using a high performance liquid chromatography (HPLC) system. Uninhibited tetrahydrofuran (THF) is used as the mobile phase at a flow rate of 1 mL/min while setting the column and detector temperature to 40°C. The sample is dissolved in the mobile phase (~1%) and filtered through a 0.45 μm PTFE membrane. Inject a 100 μL aliquot of the sample solution and analyze for a 50 min run time. Sample results are quantified using Empower Pro against a standard curve consisting of 12 narrowly distributed PEG standards (44000 - 238 Mp; Sigma-Aldrich (Fluka) ReadyCal Set). Molecular distributions reported here are relative (PEG) values.

1 , a GPC chromatogram with two peaks is shown and is generally designated as peak A, and peak B is designated by arrows A and B, respectively. In Figure 1, one peak A represents the concentration of component A, where component A is the undesirable polyether acetal polyol component. Another peak B represents the concentration of component B, where component B is the preferred polyether polyol product component.

The concentration of polyether acetal polyol was quantified by dividing the integrated area of the high molecular weight shoulder (peak A) by the total polyol peak area in the GPC chromatograms (peaks A and B) shown in FIG. 1 ; The concentrations are reported as percentages (%).

In the following examples, Polyol A is prepared via the following general procedure: A 1.8 L reactor from Mettler Toledo is used. Mettler Toledo's reaction calorimeters are also used to control both the temperature of the reactor and the agitation rate. The reactor has an inlet port for adding propylene oxide to the thermocouple, pressure transducer and 500D ISCO pump. The reactor also has a separate inlet port used to add the first 249 g of a polyether polyol starter with a number average molecular weight of 700 g/mole. After the polyether polyol starter was dried at 130° C. for 1 hour, the temperature was lowered to 50° C. under a nitrogen atmosphere fed through the same port used to feed the propylene oxide. A Karl Fischer titration of a 24-gram sample of dried polyol removed through the bottom port of the reactor shows 56 ppm of water remaining in the sample. This leads to four stages of catalyst and propylene oxide addition using the amounts described in Table II. Another reactor port is used to evacuate nitrogen at each stage until the pressure in the reactor reaches 0 Pa. Then, using a syringe, bis(3,5-bis(trifluoromethyl)phenyl)(2,4,6) through the septum in the fitting of the same port used to add the polyether polyol starter. -Inject a solution of 1 mL THF catalyst, the THF adduct of trifluorophenyl)borane. After catalyst addition, after evacuation with nitrogen of THF in the catalyst solution, the reactor is again brought to 0 Pa, all reactor ports are closed and propylene is poured into the reactor at a constant rate of 4 mL/min through the ports designated for this purpose. Start adding at a rate. The amounts of catalyst and monomer in the four stages are as set forth in Table II below:

Table II

When all of the propylene oxide has been fed to the reactor, the corresponding inlet port for propylene oxide addition is closed and digestion of unreacted monomer is allowed to proceed. 1551 grams of product are collected through the bottom port of the reactor.

Table III - Summary of Results for Examples

Comparative Example A (No Bronsted acid was used)

In Comparative Example A, Polyol A (9.9 g) and a 12 mm magnetic stir bar are added to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 750 rpm and heated in a temperature-controlled aluminum reaction block at 100° C. for 30 minutes. Next, deionized water (0.10 g) is added to the vial and the polyol-water solution in the vial is capped and stirred at 750 rpm and 100° C. for 6 hours. A sample of the vial for GPC analysis is collected 6 hours after heating and stirring the polyol solution by briefly removing the vial cap and withdrawing approximately 0.10 g of the polyol solution. A sample of the polyol solution is diluted with 10.0 g of uninhibited tetrahydrofuran (THF) and filtered through a 0.45 μm polytetrafluoroethylene (PTFE) syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table IV.

Table IV - GPC Results

As shown in Table IV, water treatment at 100° C. did not reduce the polyether acetal polyol content compared to the initial untreated sample even after a treatment time of 6 hours.

Comparative Example B (phosphoric acid is used)

Add Polyol A (9.9 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 750 rpm and heated in a temperature-controlled aluminum reaction block at 100° C. for 30 minutes. Next, phosphoric acid is added streamwise as a stock solution to deionized water (0.10 g; stock solution: 14.1 mg 85% phosphoric acid in 2.0 g deionized water) and the polyol solution is capped and stirred at 750 rpm and 100° C. for 6 hours. After 6 hours, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect GPC samples. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table V.

Table V - GPC Results

As shown in Table V, treatment with aqueous phosphoric acid solution at 100° C. did not reduce the polyether acetal polyol content compared to the initial untreated sample even after a treatment time of 6 hours.

Invention Example 1

Add Polyol A (9.9 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 750 rpm and heated in a temperature-controlled aluminum reaction block at 100° C. for 30 minutes. Next, dodecylbenzene sulfonic acid (DBSA) was added streamwise as a stock solution to water (0.10 g; stock solution: 20.0 mg DBSA and 1.0 g deionized water), capped the polyol solution and 30 min at 750 rpm and 100° C. stir while GPC samples are collected after 5 and 30 minutes by briefly removing the vial cap and withdrawing approximately 0.10 g of polyol. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values after 5 and 30 minutes is summarized in Table VI.

Table VI - GPC Results

As shown in Table VI, DBSA treatment at 100° C. reduces the polyether acetal polyol content compared to the initial untreated sample.

Invention Example 2

Add Polyol A (9.5 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 750 rpm and heated in a temperature-controlled aluminum reaction block at 100° C. for 30 minutes. Next, dodecylbenzene sulfonic acid (DBSA) was added as a stock solution in water (0.50 g; stock solution: 20.0 mg DBSA and 5.0 g deionized water) in a stream manner, the polyol solution was capped and the polyol solution was capped and held at 750 rpm and 100° C. for 5 minutes. stir while

After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. The DBSA treated polyol is capped again until the next sample is collected. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table VII.

Table VII - GPC Results

Invention example 3

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 750 rpm and heated in a temperature-controlled aluminum reaction block at 100° C. for 30 minutes. Next, dodecylbenzene sulfonic acid (DBSA) was added streamwise as a stock solution in water (0.25 g; stock solution: 10.0 mg DBSA and 5.0 g deionized water), capped the polyol solution and 5 min at 750 rpm and 100° C. stir while After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table VIII.

Table VIII - GPC Results

Invention Example 4

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 750 rpm and heated in a temperature-controlled aluminum reaction block at 80° C. for 30 minutes. Next, DBSA is added streamwise as a stock solution to water (0.25 g, stock solution: 20.0 mg DBSA and 5.0 g deionized water) and the polyol solution is capped and stirred at 750 rpm and 80° C. for 30 minutes. GPC samples are collected after 5 and 30 minutes by briefly removing the vial cap and withdrawing approximately 0.10 g of polyol. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values after 5 and 30 minutes is summarized in Table IX.

Table IX - GPC Results

Comparative Example C (Benzenesulfonic acid is used instead of DBSA)

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 350 rpm and heated in a temperature-controlled aluminum reaction block at 90° C. for 30 minutes. Next, benzenesulfonic acid (BSA) monohydrate was added streamwise as a stock solution to water (0.25 g; stock solution: 10.8 mg BSA monohydrate and 5.0 g deionized water), capped the polyol solution and at 350 rpm and 90° C. Stir for 5 minutes. After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table X.

Table X - GPC Results

Comparative Example D (pTSA was used instead of DBSA)

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 350 rpm and heated in a temperature-controlled aluminum reaction block at 90° C. for 30 minutes. Next, para toluenesulfonic acid ( p TSA) monohydrate was added streamwise as a stock solution to water (0.25 g; stock solution: 11.6 mg p TSA monohydrate and 5.0 g deionized water), the polyol solution was capped and the temperature was increased at 350 rpm and Stir at 90° C. for 5 minutes. After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table XI.

Table XI - GPC Results

Comparative Example E (4-hydroxybenzene sulfonic acid was used instead of DBSA)

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 350 rpm and heated in a temperature-controlled aluminum reaction block at 90° C. for 30 minutes. Next, 4-hydroxybenzene sulfonic acid (60% solution in water) is added streamwise as stock solution to water (0.25 g; stock solution: 19.7 mg 60% 4-hydroxybenzene sulfonic acid solution and 5.0 g deionized water) and the polyol solution is capped and stirred at 350 rpm and 90° C. for 5 minutes. After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table XII.

Table XII - GPC Results

Comparative Example F (4-chlorobenzene sulfonic acid is used instead of DBSA)

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 350 rpm and heated in a temperature-controlled aluminum reaction block at 90° C. for 30 minutes. to the next, 4-Chlorobenzene sulfonic acid (90%) was added streamwise as a stock solution to water (0.25 g; stock solution: 13.1 mg 90% 4-chlorobenzene sulfonic acid solution and 5.0 g deionized water), capped polyol solution and set at 350 rpm and at 90° C. for 5 minutes. After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table XIII.

Table XIII - GPC Results

Comparative Example G (ethanesulfonic acid is used instead of DBSA)

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 350 rpm and heated in a temperature-controlled aluminum reaction block at 90° C. for 30 minutes. Next, ethanesulfonic acid is added streamwise as a stock solution to water (0.25 g; stock solution: 6.7 mg ethanesulfonic acid and 5.0 g deionized water), the polyol solution is capped and stirred at 350 rpm and 90° C. for 5 minutes. After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table XIV.

Table XIV - GPC Results

Invention Example 5

Add Polyol A (4.75 g) and a 12 mm magnetic stir bar to a 20 mL borosilicate glass scintillation vial. The polyol is stirred at 350 rpm and heated in a temperature-controlled aluminum reaction block at 90° C. for 30 minutes. Next, DBSA is added streamwise as a stock solution in water (0.25 g, stock solution: 20.0 mg DBSA and 5.0 g deionized water), the polyol solution is capped and stirred at 350 rpm and 90° C. for 5 minutes. After 5 minutes, the vial cap is briefly removed and approximately 0.10 g of polyol is withdrawn to collect a GPC sample. Samples are diluted with 10.0 g of uninhibited THF and filtered through a 0.45 μm PTFE syringe filter for GPC analysis. The GPC analysis for polyether acetal polyol area % values is summarized in Table XV.

Table XV - GPC Results

Other implementations

One embodiment of the present invention provides a polyether polyol comprising (i) an alkyl- or arylsulfonic acid catalyst, which is a catalyst comprising a substituted or unsubstituted alkyl group of at least 6 carbon atoms, and (ii) components (i) and (ii) ) is sufficient to reduce the first residual level of acetal linkages present in the polyether polyol to a reduced second level of acetal linkages present in the polyether polyol. and a polyether polyol purification process having a first residual level of acetal linkages present in the polyol. For example, in an exemplary embodiment, the sulfonic acid catalyst is an alkylsulfonic acid catalyst. In another exemplary embodiment, the sulfonic acid catalyst is an arylsulfonic acid catalyst.

In the process described above, the C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid concentration is from 0.0001 to 0.005 moles of C6 to C18 alkylsulfonic acid or C6 to C18 alkylated arylsulfonic acid per kilogram of polyether polyol.

Another embodiment of the process described above further comprises agitating the resulting biphasic mixture with a sufficient concentration of water. In an exemplary embodiment, the concentration of water is between 0.5% and 20% by weight.

Yet another embodiment of the process described above further comprises the steps of: (A) the polyether polyol is (i) a catalyst comprising a carbon atom chain length of at least 6 carbon atoms. , an alkyl- or arylsulfonic acid catalyst, and (ii) water; and (B) heating the biphasic mixture to reduce residual levels of acetal linkages present in the polyether polyol. In one exemplary embodiment, treatment step (A) comprises a treatment reaction time of < 5 minutes.

Another embodiment of the process of the present invention relates to a polyether polyol product wherein the polyether product is an acid-finished polyether polyol produced by any of the processes described above.

Yet another embodiment of the present invention relates to a polyurethane product comprising the reaction product of a polyether polyol and an isocyanate, wherein the polyether polyol is an acid-finished polyether produced by any of the processes described above. It is a polyol.

Claims (10)

A process for purifying polyether polyols comprising:
treating the polyether polyol with a mixture of (i) a sulfonic acid catalyst comprising substituted or unsubstituted alkyl groups of at least 6 carbon atoms, and (ii) water to reduce the residual level of acetal linkages present in the polyether polyol A process comprising the step of: According to claim 1, wherein the sulfonic acid catalyst is R ⁵ -SO ₃ H or R ⁵ -ArSO ₃ H, wherein R ⁵ is a substituted or unsubstituted alkyl group having 6 to 18 carbon atoms, Ar is one of the general chemical structures of an aryl group Including, process. The process of claim 1 , wherein the concentration of water is sufficient to produce a biphasic mixture. According to claim 1,
treating the polyether polyol with the mixture; and
heating the biphasic mixture to reduce residual levels of acetal linkages present in the polyether polyol. The process according to claim 1 , wherein the residual concentration of the polyether acetal polyol present in the polyether polyol product produced by the process is reduced to less than 1.0% by weight. The process of claim 1 , wherein the sulfonic acid catalyst is dodecylbenzene sulfonic acid. 5. The process according to claim 4, wherein the treatment temperature of the treatment step (A) is between 60°C and 140°C. 5. The process according to claim 4, wherein the treatment reaction time of treatment step (A) is 30 minutes or less. The method of claim 1 , wherein the polyether polyol is produced using a Lewis acidic alkoxylation catalyst; wherein the polyether polyol is a non-finished polyol. 10. The method of claim 9, wherein the Lewis acid alkoxylation catalyst is a compound having the general formula M(R ¹ ) ₁ (R ² ) ₁ (R ³ ) ₁ (R ⁴ ) _{0 or 1} , wherein M is boron; aluminum, indium, bismuth or erbium, R ¹ , R ² , R ³ , and R ⁴ are each independently, R ¹ comprises a first fluoro/chloro or fluoroalkyl-substituted phenyl group, R ² represents a second fluoro/chloro or fluoroalkyl-substituted phenyl group wherein R ³ comprises a third fluoro/chloro or fluoroalkyl-substituted phenyl group or a first functional group or functional polymer group, and optionally R ⁴ is a second functional group or functional polymer group.

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